JP2007217681A - Method for producing azo compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method for safely synthesizing an azo dye compound from an easily available and synthesizable raw material under a mild reaction condition in high yield. <P>SOLUTION: The method for the production of an azo compound has a step (a) to mix a diazotizing agent, an acid or mixed acid having a Hammett acidity function H<SB>0</SB>of ≤-1.00, and an amino compound and a step to mix the prepared diazonium compound liquid obtained by the step (a) with a compound expressed by general formula (1) (X is H or a substituent; Y is -OR<SP>1</SP>, -NR<SP>2</SP>R<SP>3</SP>or -SR<SP>4</SP>; R<SP>1</SP>is H, an alkali metal ion, an organic cation, an aliphatic group, an aryl group or a heterocyclic group; R<SP>2</SP>to R<SP>4</SP>are each hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group; Z is -OM or -NR<SP>5</SP>R<SP>6</SP>; M is H or a metal ion; R<SP>5</SP>and R<SP>6</SP>are each H, an aliphatic group, an aryl group, a heterocyclic group or the like; G is H or a halogen atom; Q is an atomic group constituting a nitrogen-containing heterocyclic group; and N, s and t are integers satisfying the formulas 1≤n≤3, 0≤s≤2, 0≤t≤1 and n+s+t=3). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing an azo compound.

  Various methods for synthesizing azo compounds have been known for a long time. Synthesis and reduction by oxidation reaction as described in New Experimental Chemistry Course (Maruzen Co., Ltd.) Volume 14-III, pages 1516 to 1534 There were synthesis by reaction, synthesis by substitution reaction, synthesis by addition reaction, synthesis by condensation reaction, and other synthesis methods. However, it is used as an industrial production method of azo dye compounds because of the azo coupling reaction between diazonium compounds and coupling components such as anilines and phenols from the viewpoints of availability of raw materials, cost, and yield. However, this method also has drawbacks such as the risk of explosion of the diazonium compound and a low yield depending on the type of the diazonium compound and the coupling component. Specifically, a diazonium compound having an electron-withdrawing group bonded thereto is difficult to produce and requires a reaction under strong acidity, so it cannot be applied when an acidic and unstable functional group exists, There are major limitations. In particular, heterocyclic diazonium compounds are often unstable, and a highly general synthesis method is not known. Furthermore, it is known that the coupling component reacts efficiently in the diazo coupling method when the coupling reaction position is unsubstituted or a formyl group, a carboxyl group, or the like is bonded. However, it is known that almost no dye is formed with a coupling component in which a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, an aryloxy group or an acyloxy group is bonded.

  As another method, a method of synthesizing an azo dye compound by reacting a sulfonylhydrazine compound described in European Patent Nos. 545491A1 and 565165A1 with a coupling component in a photosensitive material is also known. In this method, as in the case of the diazonium compound, as the coupling component, the position of the coupling reaction is unsubstituted, or only a limited group such as a formyl group or a carboxyl group reacts efficiently. In this case, the yield was low.

  As described above, the conventional methods for synthesizing azo compounds have problems such as availability of raw materials, risk of explosion, limitation of application range, and often low yield. The object of the present invention is to overcome the above-mentioned problems and to provide a production method capable of synthesizing an azo dye compound safely and under mild reaction conditions and in a high yield from raw materials that can be easily obtained and synthesized. There is.

As a result of intensive studies in view of the above problems, the present inventors have found that the production of an azo compound can be achieved in a high yield by improving the reaction rate in step (a) described later. In general production of a diazonium compound, a diazotizing compound is obtained by adding a diazotizing agent to a solution obtained by dissolving or suspending the corresponding amino compound in an acidic solvent. Depending on the amino compound, diazonium compound is obtained by this method. A compound may not be obtained. Although details of the cause are unknown, [1] completely dissolving the amino compound used in step (a), [2] stabilizing the diazonium compound to be formed, and [3] (b) described later In the process, it was found that it is important to improve the yield to suspend or dissolve the compound represented by the general formula (1) to be reacted with a solvent and mix it with the diazonium compound adjusting solution in the process (a). [1] and [2] were able to solve the above problems by using a strong acid and using an alcohol or an organic acid (or a mixture of alcohol and organic acid) as the solvent used in [3]. Furthermore, it was found that when the unreacted diazotizing agent was eliminated with a deactivator after induction into a diazonium compound, the yield was increased.
In addition, when a heating and stirring step is introduced as the step (c) after the steps (a) and (b) in the method for producing an azo compound of the present invention, the filterability when separating the azo compound (crystallized product) from the reaction solution is improved. Succeeded in improving dramatically. Compared with the method of separating the azo compound (crystallized product) after the step (b), the filterability when separating the azo compound (crystallized product) from the reaction solution after the step (c) is greatly improved.

  The present invention is as follows.

1. (A) a step of mixing an acid or mixed acid and an amino compound having an acidity function H ₀ of the diazotizing agent and Hammett of −1.00 or less; a diazonium compound adjusting liquid obtained in the step (a); A method for producing an azo compound, comprising the step of compound (b) represented by (1).

In the above general formula (1):
Each X independently represents a hydrogen atom or a substituent, and this substituent may further have a substituent.
Y represents —OR ¹ , —NR ² R ³ , or —SR ⁴ , and R ¹ represents a hydrogen atom, an alkali metal ion, an organic cation, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic ring. R ^{2 to} R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. These groups may further have a substituent.
Z represents —OM or —NR ⁵ R ⁶ . M represents a hydrogen atom or a metal ion, and R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkyl or arylcarbonyl group, or Represents an alkyl or arylsulfonyl group; These groups may further have a substituent.
G represents a hydrogen atom or a halogen atom.
Q represents an atomic group constituting a nitrogen-containing heterocyclic ring together with a carbon atom directly connected to pyrazole.
n, s, and t represent integers satisfying the relationships of 1 ≦ n ≦ 3, 0 ≦ s ≦ 2, 0 ≦ t ≦ 1, and n + s + t = 3.

2. 2. The method for producing an azo compound according to 1, wherein in formula (1), the nitrogen-containing heterocycle formed by Q is a 5- or 6-membered aromatic nitrogen-containing heterocycle.

3. The method for producing an azo compound according to 1 or 2, wherein the general formula (1) is the following general formula (2).

In the general formula (2):
Each X independently represents a hydrogen atom or a substituent, and this substituent may further have a substituent.
Y represents —OR ¹ , —NR ² R ³ , or —SR ⁴ , and R ¹ represents a hydrogen atom, an alkali metal ion, an organic cation, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic ring. R ^{2 to} R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. These groups may further have a substituent.
Z represents —OM or —NR ⁵ R ⁶ . M represents a hydrogen atom or a metal ion, and R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkyl or arylcarbonyl group, or Represents an alkyl or arylsulfonyl group; These groups may further have a substituent.
G represents a hydrogen atom or a halogen atom.
n, s, and t represent integers satisfying the relationships of 1 ≦ n ≦ 3, 0 ≦ s ≦ 2, 0 ≦ t ≦ 1, and n + s + t = 3.

4). In the said General formula (1) or General formula (2), n is 2 or 3, The manufacturing method of the azo compound as described in any one of 1-3 characterized by the above-mentioned.

5. The said general formula (2) is following General formula (3), The manufacturing method of the azo compound as described in any one of 1-4 characterized by the above-mentioned.

In the general formula (3):
X ¹ and X ² each independently represent a hydrogen atom or a substituent, and this substituent may further have a substituent.
Y represents —OR ¹ , —NR ² R ³ , or —SR ⁴ , and R ¹ represents a hydrogen atom, an alkali metal ion, an organic cation, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic ring. R ^{2 to} R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. These groups may further have a substituent.
Z ¹ and Z ² each independently represent —OM or —NR ⁵ R ⁶ . M represents a hydrogen atom or a metal ion, and R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkyl or arylcarbonyl group, or Represents an alkyl or arylsulfonyl group; These groups may further have a substituent.

6). The said amino compound is an amino pyrazole derivative and its salt, The manufacturing method of the azo compound as described in any one of 1-5 characterized by the above-mentioned.

7). The said amino compound is General formula (4), The manufacturing method of the azo compound as described in any one of 1-6 characterized by the above-mentioned.

In the general formula (4), R ¹¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group or a heterocyclic group, and R ¹² represents a hydrogen atom or a Hammett substituent constant. σp value represents a substituent having a value of 0.20 or more, and R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a substituent. Two or more of R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ represent an ionic hydrophilic group or a monovalent group having an ionic hydrophilic group as a substituent. However, the case where R ¹³ and R ¹⁶ are simultaneously a sulfo group is excluded.

8). 8. The method for producing an azo compound according to 7, wherein in the general formula (4), R ¹² is a cyano group, —SO ₂ CH ₃ or —SO ₂ Ph.

9. The method for producing an azo compound according to 7 or 8, wherein in the general formula (4), R ¹² is a cyano group.

10. The method for producing an azo compound according to any one of 1 to 9, wherein in the step (a), the diazotizing agent is nitrosylsulfuric acid.

11. The azo compound according to any one of 1 to 10, wherein in the step (a), the acid is sulfuric acid, phosphoric acid, or methanesulfonic acid, and the mixed acid is a mixed acid of these acids and acetic acid. Manufacturing method.

12 The method for producing an azo compound according to any one of 1 to 11, further comprising a step (c) of stirring the mixed liquid obtained in the step (b) while heating.

13. The azo compound according to the following general formula (5), obtained by the production method according to any one of 1 to 12.

In the general formula (5):
Q ¹ and Q ² each independently represents an aromatic hydrocarbon ring group, a non-aromatic hydrocarbon ring group, an aromatic heterocyclic group or a non-aromatic heterocyclic group, which may have a substituent, and X ¹ and X ² each independently represents a hydrogen atom or a substituent, and this substituent may further have a substituent.
Y represents —OR ¹ , and R ¹ represents a hydrogen atom or a metal ion. Z ¹ and Z ² each independently represent —OM or —NR ⁵ R ⁶ . M represents a hydrogen atom or a metal ion, and R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkyl or arylcarbonyl group, or Represents an alkyl or arylsulfonyl group; These groups may further have a substituent.

  ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing an azo compound useful for each field | areas, such as industry, agriculture, medical treatment, and science, can be provided with a high yield and low cost.

  Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto.

  First, the details of the step (a) according to the present invention will be described.

In the step (a), the diazonium compound is converted into a diazonium compound by a reaction between the amino compound and the diazotizing agent by mixing an acid or a mixed acid and an amino compound having an acidity function H ₀ of the diazotizing agent and Hammett of −1.00 or less. Induced in liquid. In the present application, the liquid containing the diazonium compound is referred to as “diazonium compound adjusting liquid”. The method of mixing the amino compound, the acid and the diazotizing agent is not particularly limited, but it is preferable to add the amino compound to the diazotizing agent and acid solution.
The diazotizing agent in step (a) is used for deriving an amino compound into a diazonium compound, and is not limited as long as it has such an action. Representative examples of the diazotizing agent include nitrites (for example, sodium nitrite and potassium nitrite), isoamyl nitrite and nitrosylsulfuric acid, more preferably sodium nitrite, potassium nitrite and nitrosylsulfuric acid. Among them, nitrosylsulfuric acid is particularly preferable.

The acid used in the step (a) means an acid that can be dissolved even if it does not completely dissolve the amino compound, and preferably an acid that completely dissolves the amino compound. As the acid, an inorganic acid (also called a mineral acid) and an organic acid can be used. Examples of the inorganic acid include hydrochloric acid, phosphoric acid, and sulfuric acid, preferably phosphoric acid and sulfuric acid, and more preferably sulfuric acid. Examples of the organic acid include formic acid, acetic acid, propionic acid, and methanesulfonic acid, preferably acetic acid, propionic acid, and methanesulfonic acid, and more preferably acetic acid and methanesulfonic acid. These acids may be used alone or in combination. Examples of the mixed acid include phosphoric acid / acetic acid, sulfuric acid / acetic acid, methanesulfonic acid / acetic acid, acetic acid / propionic acid, and preferably sulfuric acid / acetic acid, sulfuric acid / propionic acid, sulfuric acid / acetic acid / propionic acid, methanesulfonic acid / Acetic acid, more preferably sulfuric acid / acetic acid, sulfuric acid / acetic acid / propionic acid, among which sulfuric acid / acetic acid is particularly preferable. 1 / (0.1-20) is preferable, as for the mass ratio of these mixed acids, 1 / (0.5-10) is more preferable, More preferably, it is 1 / (1-10). Further, the mixed acid may be three or more. For example, sulfuric acid / acetic acid / propionic acid [mass ratio is preferably 1 / (0.5 to 10) / (0.5 to 10)], methanesulfonic acid / acetic acid / propionic acid [mass ratio is 1 / (0 0.5-10) / (0.5-10) is preferred].

Using acidity function _{H 0} of Hammett, _{H 0} at 25 ° C. of an acid or a mixed acid is at -1.00 or less, preferably -1.05 or less, more preferably is -1.10 or less .

The acidity function in the present specification is also called Hammett acidity function as described in detail in “New Experimental Chemistry Course 3rd Edition, Vol. 1, p.213-216”. Represents a measure of the ability to donate H ⁺ . Especially used to measure the pH of acidic thick solutions. The hydrogen ions H ⁺ of activity a _{H +,} electrically activity coefficient f _B of neutral weak base _B, concentration c _B, the activity coefficient of BH ⁺ its conjugate acid f _{BH +,} the concentration c _{BH +,} if the acid dissociation constant and pKa, acidity function _{H 0} is expressed by the following equation.
H ₀ = −log ₁₀ (a _{H +} f _B / f _{BH +} ) = pKa + log ₁₀ (c _B / c _{BH +} )
pKa = −log ₁₀ (a _{H +} a _B / a _{BH +} )
It is. Since f _B / f _{BH +} is constant for many bases, H ₀ is a measure of the strength of the solution as an acid, regardless of the type of base. As H ₀ is negative and the absolute value is larger, the acid is stronger. When c _B / c _{BH +} is determined by absorptiometric method using a strongly acidic solution of 2,4,6-trinitroaniline having a pKa known, for example, pKa = -10.10, H _{0 of the} solution is determined. In addition, another base is dissolved in a solution in which H ₀ is found to obtain c _B / c _{BH +,} and pKa of BH ⁺ is obtained. In other words, it is important to determine the strength of weak bases. 40,60,80% (mass) sulfuric acid at 25 ° C. has a H ₀ of −2.54, −4.51 and −7.52. When B has a positive or negative charge, acidity functions of H ₊ and H ₋ are defined, respectively.

In the step (a), the amount of acid added to the amino compound is 1 to 100 times, more preferably 2 to 50 times, and still more preferably 3 to 25 times in terms of mass ratio. When the mass ratio is less than 1 time, the stirring ability is deteriorated and the diazonium compound cannot be induced. On the other hand, when the mass ratio is 100 times or more, the productivity becomes poor and uneconomical.
Moreover, the addition amount of the diazotizing agent with respect to the amino compound in the step (a) is 1.0 to 20 times, more preferably 1.0 to 10 times, and further 1.0 to 5 times in terms of molar ratio. preferable. A diazotizing agent having a molar ratio of at least 1 is necessary to derive a diazonium compound, and if it is 20 times or more, the diazonium compound is decomposed by a side reaction.

In the mixing of the diazotizing agent, acid and amino compound in the step (a), it is preferably carried out at 20 ° C. or less, more preferably at 15 ° C. or less, further preferably at 12 ° C. or less. Is desirable. There is a concern about the decomposition of the diazotizing agent in the adjustment of the diazo liquid at 20 ° C. or higher. The stirring time for inducing the diazonium compound is preferably 0.3 to 10 hours, more preferably 0.5 to 5 hours, and further preferably 1 to 3 hours. In 0.3 hours or less, it is difficult to induce completely, and in 10 hours or more, there is a concern about the decomposition of the diazonium compound. Moreover, a normal stirrer is used for mixing, and there is no limitation in particular. Although depending on the production equipment, the preferred stirring speed is preferably 30 to 300 rpm, more preferably 40 to 200 prm, and still more preferably 50 to 200 rpm. When the stirring speed is 30 rpm or less, the stirring efficiency of the diazonium compound adjusting solution is deteriorated, and there is a concern that the desired reaction proceeds.

The solvent that can be mixed in the step (a) is not particularly limited as long as the derived diazonium compound is not decomposed. Examples of miscible solvents include hydrocarbon solvents such as hexane, benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, ketone solvents such as acetone and methyl ethyl ketone, dimethylformamide, dimethylacetamide, pyrrolidone and N-methyl- Examples include amide solvents such as 2-pyrrolidone, dimethyl sulfoxide, sulfolane, and acetonitrile.

  The order of adding amino compounds is not limited as long as no precipitation of amino compounds occurs. The preferred order of addition is first the diazotizing agent and acid followed by the amino compound. If the generation of diazonium compound is not suppressed by precipitation of amino compound as mentioned above, it is possible to mix amino compound and acid first, and finally add diazotizing agent, and diazotize in acid. A method of simultaneously adding the agent and the amino compound is also possible.

The preferred pH of the diazonium compound adjusting solution in step (a) is preferably 7 or less, more preferably 5 or less, and even more preferably 3 or less. When the pH of the diazonium compound adjusting solution in the step (a) is 7 or more, there is a concern about the decomposition of the induced diazonium compound.

The amino compound used in the step (a) means an amino compound having a ring that may have a substituent, and includes a single ring and a condensed ring. The aforementioned rings include aromatic hydrocarbon rings, non-aromatic hydrocarbon rings, aromatic heterocycles, or non-aromatic heterocycles. Among them, an aromatic heterocyclic amino compound or a non-aromatic heterocyclic amino compound is preferable, an aromatic heterocyclic amino compound is more preferable, and a nitrogen-containing 5- to 7-membered aromatic heterocyclic amino compound is more preferable. In the amino compound having a ring which may have a substituent, preferred examples of the ring include a benzene ring, an imidazole ring, a benzimidazole ring, a pyrazole ring, a benzopyrazole ring, a triazole ring, a thiazole ring, a benzothiazole ring, Thiazole ring, benzoisothiazole ring, oxazole ring, benzoxazole ring, thiadiazole ring, pyrrole ring, benzopyrrole ring, indole ring, isoxazole ring, benzoisoxazole ring, thiophene ring, benzothiophene ring, furan ring, pyran ring, A benzofuran ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a cinnoline ring, a phthalazine ring, a quinazoline ring, a quinoxaline ring, or a triazine ring. However, the substitution position of the amino group and the substituent of the ring and the substitution position are not limited. In the amino compound having a ring, more preferable examples of the ring include 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-aminopyrimidine, 4-aminopyrimidine, 5-aminopyrimidine, 3-aminopyridazine, 4-aminopyridine, Aminopyridazine, 2-aminopyrrole, 3-aminopyrrole, 2-aminoimidazole, 4-aminoimidazole, 3-aminopyrazole, 4-aminopyrazole, 5-aminopyrazole, 4-aminotriazole, 4-amino-1,2 , 3-triazole, 3-amino-1,2,4-triazole, 2-aminooxazole, 4-aminooxazole, 5-aminooxazole, 3-aminoisoxazole, 4-aminoisoxazole, 5-aminoisoxazole, 2-aminothiazole, 4-aminothi Sol, 5-aminothiazole, 3-aminoisothiazole, 4-aminoisothiazole, 5-aminoisothiazole, 2-amino-1,3,4-thiadiazole, 3-amino-1,2,4-thiadiazole, or 5-amino-1,2,4-thiadiazole, more preferred examples include 2-aminopyrrole, 3-aminopyrrole, 3-aminopyrazole, 4-aminopyrazole, 5-aminopyrazole, 2-aminothiazole, 4 -Aminothiazole, 5-aminothiazole, 2-amino-1,3,4-thiadiazole, 3-amino-1,2,4-thiadiazole, or 5-amino-1,2,4-thiadiazole, 5-aminopyrazole, 2-amino-1,3,4-thiadiazole, or 5-amino-1,2,4- Particularly preferred thiadiazole, 5-aminopyrazole being most preferred.

  In addition, the amino compound used in step (a) may form a dimer linked by L (a divalent linking group).

The divalent linking group represented by L includes an oxy group —O—, a thio group —S—, a carbonyl group —CO—, a sulfonyl group —SO ₂ —, an imino group —NH—, a methylene group —CH ₂ —, A phenylene group -Ph-, a heterocyclic group, and a group formed by combining these groups. Examples of the group formed by a combination of linking groups include urea, triazine, 1,3-diaminopropane, and 1,4-phenylene. Examples include diamines.

As the amino compound used in the step (a), a compound represented by the following general formula (4) is particularly preferable.
Next, the compound represented by formula (4) according to the present invention will be described in detail.

In the general formula (4) of the present invention, R ¹¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group or a heterocyclic group.

In the general formula (4) of the present invention, R ¹² represents a hydrogen atom or a substituent having Hammett's substituent constant σp value of 0.20 or more.

In the general formula (4) of the present invention, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ each independently represents a hydrogen atom or a substituent. Two or more of R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ represent an ionic hydrophilic group or a monovalent group having an ionic hydrophilic group as a substituent. However, the case where R ¹³ and R ¹⁶ are simultaneously a sulfo group is excluded.

Details of the general formula (4) will be described below.
R ¹¹ represents a hydrogen atom, an alkyl group, or an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, or a heterocyclic group. R ¹¹ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom.

R ¹² represents a hydrogen atom or a substituent having Hammett's substituent constant σp value of 0.20 or more. Specific examples of R ¹² having a substituent σp value of 0.20 or more include acyl group, acyloxy group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, Diarylphosphono group, diarylphosphinyl group, alkylthio group, arylthio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, A halogenated alkyl group, a halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another substituent having a σp value of 0.20 or more, a heterocyclic group, Haloge Atom, an azo group, and selenocyanate group. R ¹² is preferably a cyano group, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, or a halogen atom, more preferably a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group. And most preferably a cyano group, an alkylsulfonyl group, or an arylsulfonyl group. Of these, a cyano group is most preferred.

  Here, Hammett's substituent constant σp value used in this specification will be described. Hammett's rule is an empirical rule proposed by L. P. Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. Substituent constants determined by Hammett's rule include σp value and σm value, and these values can be found in many general books. For example, JA Dean edition, “Lange's Handbook of Chemistry” 12th edition, 1979 (Mc Graw-Hill), “Chemical domain” extra edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp. This can be found in the above-mentioned book, when it is limited only to a substituent having a known value in the literature. Needless to say, it also includes a substituent that would be included in the measurement range based on the Hammett rule even if the value is unknown. In the present invention, the σp value is used in this sense.

R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a substituent. The substituent is preferably a halogen atom, an alkyl group, an aryl group, a cyano group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an arylcarbonyl group, or an ionic hydrophilic group, more preferably a halogen atom. An atom, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an arylcarbonyl group, or an ionic hydrophilic group, and most preferably an ionic hydrophilic group. Two or more of R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ represent ionic hydrophilic groups, except for the case where R ¹³ and R ¹⁶ are both sulfo groups. A preferred ionic hydrophilic group is a carboxyl group, a sulfo group, a phosphono group, or a quaternary ammonium group, more preferably a carboxyl group or a sulfo group, and particularly preferably a carboxyl group. When R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ are a carboxyl group, a sulfo group, and a phosphono group, they may be in a salt state, and examples of counter ions that form a salt include ammonium ions, Alkali metal ions (lithium ions, sodium ions, potassium ions more preferably lithium ions, potassium ions), alkaline earth metal ions (beryllium ions, magnesium ions, calcium ions more preferably magnesium ions), organic cations (eg, ⁺ NH (C ₂ H ₅ ) ₃ , tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium ion, more preferably ⁺ NH (C ₂ H ₅ ) ₃ ). The counter ion is preferably an ammonium ion or an alkali metal ion, and more preferably an alkali metal ion.

In summary, the general formula (4) of the present invention is preferably composed of the following combinations (a) to (c).
(A) R ¹¹ represents a hydrogen atom, an alkyl group, or an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, or a heterocyclic group. R ¹¹ is preferably a hydrogen atom, an alkyl group, an alkylthio group, or an arylthio group, more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom. .
(B) R ¹² is a hydrogen atom or a substituent having Hammett's substituent constant σp value of 0.20 or more, and preferred R ¹² is a cyano group, carbamoyl group, alkoxycarbonyl group, alkylsulfonyl group, arylsulfonyl group Or a halogen atom, more preferably a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group, and most preferably a cyano group, an alkylsulfonyl group, or an arylsulfonyl group. Of these, a cyano group is most preferred.
(C) R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ each independently represents a hydrogen atom or a substituent. The substituent is preferably a halogen atom, an alkyl group, an aryl group, a cyano group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an arylcarbonyl group, or an ionic hydrophilic group, more preferably a halogen atom. An atom, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an arylcarbonyl group, or an ionic hydrophilic group, and most preferably an ionic hydrophilic group.
A preferred ionic hydrophilic group is a carboxyl group, a sulfo group, a phosphono group, or a quaternary ammonium group, more preferably a carboxyl group or a sulfo group, and particularly preferably a carboxyl group, in the case of forming a salt. Examples of the counter ion are preferably an ammonium ion, an alkali metal ion, or an organic cation. The counter ion is preferably an ammonium ion or an alkali metal ion, and more preferably an alkali metal ion. Among the alkali metal ions, lithium ions, sodium ions, or potassium ions are more preferable, and lithium ions or potassium ions are more preferable.
In addition, about the preferable combination of a substituent of the compound represented by General formula (4), the compound whose at least 1 of a various substituent is the said preferable group is preferable, and many more various substituents are the said preferable. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups described above.

  Among the compounds represented by the general formula (4), a compound represented by the following general formula (6) is more preferable.

In the formula, R ¹¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, or a heterocyclic group.

R ¹¹ is preferably a hydrogen atom or an alkyl group, an alkylthio group, an arylthio group or a heterocyclic group, more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, particularly preferably. It is a hydrogen atom.

  Hereinafter, the present invention will be described in more detail with reference to specific examples of 5-aminopyrazole, but the present invention is not limited thereto.

[Compound Example 1]

[Compound Example 2]

[Compound Example 3]

[Compound Example 4]

The substituent used in this specification will be described. The following groups are mentioned as a substituent used in this specification.
For example, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group , Acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or aryl Sulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl Aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, ionic hydrophilic group Take as an example.

  The details of the substituent will be described below.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

  Examples of the alkyl group include linear, branched, and cyclic substituted or unsubstituted alkyl groups, and also include cycloalkyl groups, bicycloalkyl groups, and tricyclo structures having many ring structures. An alkyl group (for example, an alkyl group of an alkoxy group or an alkylthio group) in a substituent described below also represents such an alkyl group. Specifically, the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, excluding substituents, more preferably an alkyl group having 1 to 20 carbon atoms, and substitution or substitution having 1 to 15 carbon atoms. An unsubstituted alkyl group is preferred. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, an n-octyl group, an eicosyl group, a 2-chloroethyl group, a 2-cyanoethyl group, and a 2-ethylhexyl group. The cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, and more preferably a cycloalkyl group having 3 to 20 carbon atoms, excluding the substituent. More preferred are 3 to 15 cycloalkyl groups. Preferable examples of the cycloalkyl group include a cyclohexyl group, a cyclopentyl group, a 4-n-dodecylcyclohexyl group, and the like, and the bicycloalkyl group is preferably a substituent having 5 to 30 carbon atoms or a substituent or a substituent. An unsubstituted bicycloalkyl group is preferable, a bicycloalkyl group having 5 to 20 carbon atoms is more preferable, and a bicycloalkyl group having 5 to 15 carbon atoms is still more preferable. That is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, a bicyclo [1,2,2] heptan-2-yl group, bicyclo [2,2,2] octane-3 -An yl group etc. are mentioned. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  Examples of the alkenyl group include linear, branched, and cyclic substituted or unsubstituted alkenyl groups, and include cycloalkenyl groups and bicycloalkenyl groups. Specifically, the alkenyl group is preferably substituted or unsubstituted having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 15 carbon atoms, excluding the substituent of the alkenyl group. Alkenyl groups such as vinyl group, allyl group, prenyl group, geranyl group, oleyl group, etc., and the cycloalkenyl group preferably has 3 to 30 carbon atoms in a state where the substituent of the cycloalkenyl group is removed. More preferably, it is a substituted or unsubstituted cycloalkenyl group having 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms. That is, the monovalent group which removed one hydrogen atom of the C3-C30 cycloalkene, for example, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, etc. are mentioned, As a bicycloalkenyl group, Is preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, and still more preferably 5 to 15 carbon atoms, excluding the substituent of the bicycloalkenyl group. . That is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond, for example, a bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] An oct-2-en-4-yl group and the like can be mentioned. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 15 carbon atoms, excluding the alkynyl group substituent. Examples include ethynyl group, propargyl group, trimethylsilylethynyl group and the like. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The aralkyl group includes an aralkyl group having a substituent and an unsubstituted aralkyl group. As the aralkyl group, a substituted or unsubstituted aralkyl group having 7 to 30, more preferably 7 to 20, and further preferably 7 to 15 carbon atoms when a substituent is excluded is preferable. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 15 carbon atoms, excluding the substituent of the aryl group. is there. For example, a phenyl group, p-tolyl group, naphthyl group, m-chlorophenyl group, o-hexadecanoylaminophenyl group and the like can be mentioned. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The heterocyclic group is preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a heterocyclic ring. It is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and still more preferably 3 to 15 carbon atoms, excluding the substituent of the group. For example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group and the like can be mentioned. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms, excluding the substituent of the alkoxy group. Examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, and a 2-methoxyethoxy group. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The aryloxy group is preferably a substituted or unsubstituted aryl having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 15 carbon atoms, excluding the aryloxy group substituent. Represents an oxy group, and examples thereof include a phenoxy group, a 2-methylphenoxy group, a 4-t-butylphenoxy group, a 3-nitrophenoxy group, and a 2-tetradecanoylaminophenoxy group. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The silyloxy group is preferably a substituted or unsubstituted silyloxy group having 0 to 20 carbon atoms, more preferably 0 to 20 carbon atoms, still more preferably 0 to 15 carbon atoms, excluding the substituent of the silyloxy group. Examples thereof include a trimethylsilyloxy group and a diphenylmethylsilyloxy group. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.

  The heterocyclic oxy group is preferably substituted or unsubstituted having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 15 carbon atoms, excluding the substituents of the heterocyclic oxy group. And includes, for example, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group and the like. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms without a substituent, and 6 to 30 carbon atoms without a substituent. A substituted or unsubstituted arylcarbonyloxy group having 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms is more preferable. Examples thereof include an acetyloxy group, a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, and a p-methoxyphenylcarbonyloxy group. Examples of the substituent include an alkyl group and an aryl group.

  The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 15 carbon atoms, excluding the substituent of the carbamoyloxy group. Oxy groups such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group Etc. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.

  The alkoxycarbonyloxy group is preferably substituted or unsubstituted having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 15 carbon atoms, excluding the alkoxycarbonyloxy group substituent. Examples thereof include an alkoxycarbonyloxy group such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, and an n-octylcarbonyloxy group. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The aryloxycarbonyloxy group is preferably a substituent having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, still more preferably 7 to 15 carbon atoms, excluding the aryloxycarbonyloxy group substituent. An unsubstituted aryloxycarbonyloxy group, for example, phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group and the like can be mentioned. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The amino group includes an alkylamino group, an arylamino group, and a heterocyclic amino group, and preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, more preferably 1 to 20 carbon atoms, excluding the amino group and substituent. A substituted or unsubstituted alkylamino group having 1 to 15 carbon atoms, and having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, excluding the substituent group; Examples thereof include a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, and a diphenylamino group. Examples of the substituent include an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15 carbon atoms excluding the substituent, A substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 15 carbon atoms, excluding substituents, such as acetylamino group, pivaloylamino group, lauroyl An amino group, a benzoylamino group, a 3,4,5-tri-n-octyloxyphenylcarbonylamino group, etc. are mentioned. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The aminocarbonylamino group is preferably a substituted or unsubstituted group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 15 carbon atoms, excluding the aminocarbonylamino group substituent. Aminocarbonylamino group, for example, carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group and the like. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.

  The alkoxycarbonylamino group is preferably substituted or unsubstituted having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 15 carbon atoms, excluding the alkoxycarbonylamino group substituent. Represents an alkoxycarbonylamino group, and examples thereof include a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, and an N-methyl-methoxycarbonylamino group. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The aryloxycarbonylamino group is preferably a substituent having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and still more preferably 7 to 15 carbon atoms, excluding the aryloxycarbonylamino group substituent. It represents an unsubstituted aryloxycarbonylamino group, and examples thereof include a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, and an mn-octyloxyphenoxycarbonylamino group. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The sulfamoylamino group is preferably a substituent having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, still more preferably 0 to 15 carbon atoms, excluding the substituent of the sulfamoylamino group. An unsubstituted sulfamoylamino group, for example, sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group and the like can be mentioned. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.

  The alkyl or arylsulfonylamino group is preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15 carbon atoms excluding the substituent. A substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 15 carbon atoms. Examples thereof include a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, and a p-methylphenylsulfonylamino group. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The alkylthio group is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 15 carbon atoms, excluding the substituent of the alkylthio group, For example, a methylthio group, an ethylthio group, an n-hexadecylthio group, etc. are mentioned. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The arylthio group is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, excluding the arylthio group substituent. For example, a phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group, etc. are mentioned. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The heterocyclic thio group is preferably substituted or unsubstituted having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 15 carbon atoms, excluding the substituent of the heterocyclic thio group. Heterocyclic thio groups such as 2-benzothiazolylthio group and 1-phenyltetrazol-5-ylthio group. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, still more preferably 0 to 15 carbon atoms, excluding the substituent of the sulfamoyl group, For example, N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group and the like can be mentioned. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.

  The alkyl or arylsulfinyl group is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15 carbon atoms excluding the substituent, A substituted or unsubstituted arylsulfinyl group having 6 to 30, more preferably 6 to 20, more preferably 6 to 15 carbon atoms excluding a substituent, such as a methylsulfinyl group, an ethylsulfinyl group, or a phenylsulfinyl group And p-methylphenylsulfinyl group. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The alkyl or arylsulfonyl group is preferably a substituted or unsubstituted alkylsulfonyl group or substituent having 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15 carbon atoms excluding the substituent. A substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p -A methylphenylsulfonyl group etc. are mentioned. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The acyl group is preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, more preferably 2 to 20, and even more preferably 2 to 15 carbon atoms excluding substituents. 7 to 30, more preferably 7 to 20, more preferably 7 to 15 carbon atoms, and more preferably 7 to 15 carbon atoms, and 2 to 30 carbon atoms excluding substituents. A heterocyclic carbonyl group, preferably an acetyl group, a pivaloyl group, a 2-chloroacetyl group, a stearoyl group, which is bonded to a carbonyl group with 2 to 20, more preferably 2 to 15 substituted or unsubstituted carbon atoms, A benzoyl group, a pn-octyloxyphenylcarbonyl group, a 2-pyridylcarbonyl group, a 2-furylcarbonyl group, and the like. . Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.

  The aryloxycarbonyl group is preferably substituted or unsubstituted having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, still more preferably 7 to 15 carbon atoms, excluding the aryloxycarbonyl group substituent. Aryloxycarbonyl group, for example, phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt-butylphenoxycarbonyl group, and the like. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 15 carbon atoms, excluding the alkoxycarbonyl group substituent. Groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, an n-octadecyloxycarbonyl group, and the like. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms, excluding the carbamoyl group substituent. For example, a carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group and the like can be mentioned. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.

  The aryl or heterocyclic azo group is preferably a substituted or unsubstituted arylazo group or substituent having 6 to 30, more preferably 6 to 20, more preferably 6 to 15 carbon atoms excluding the substituent. A substituted or unsubstituted heterocyclic azo group having 3 to 30, more preferably 3 to 20, more preferably 3 to 15 carbon atoms in the excluded state, such as phenylazo, p-chlorophenylazo, 5-ethylthio-1, 3,4-thiadiazol-2-ylazo and the like can be mentioned. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  The imide group is preferably a substituted or unsubstituted imide group having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, still more preferably 0 to 15 carbon atoms, excluding the substituent of the imide group. N-succinimide group, N-phthalimide group and the like. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.

The phosphino group is preferably a substituted or unsubstituted phosphino group having 0 to 30, more preferably 0 to 20, more preferably 0 to 15 carbon atoms excluding the substituent, such as a dimethylphosphino group. , Diphenylphosphino group, methylphenoxyphosphino group and the like.
The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 0 to 30, more preferably 0 to 20, more preferably 0 to 15 carbon atoms excluding the substituent, for example, phosphinyl group, dioctyl. Examples thereof include an oxyphosphinyl group and a diethoxyphosphinyl group. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.

  As the phosphinyloxy group, a substituted or unsubstituted phosphinyloxy group having preferably 0 to 30, more preferably 0 to 20, and even more preferably 0 to 15 carbon atoms excluding the substituent, For example, a diphenoxyphosphinyloxy group, a dioctyloxyphosphinyloxy group, etc. are mentioned. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.

  The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 0 to 30, more preferably 0 to 20, and even more preferably 0 to 15 carbon atoms excluding the substituent, Examples thereof include a dimethoxyphosphinylamino group and a dimethylaminophosphinylamino group. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.

  The silyl group is preferably a substituted or unsubstituted silyl group having 0 to 30, more preferably 0 to 20, more preferably 0 to 15 carbon atoms excluding substituents, such as a trimethylsilyl group, t -A butyldimethylsilyl group, a phenyldimethylsilyl group, etc. are mentioned. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.

Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a carboxyl group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, lithium ion, sodium ion, potassium ion) and organic cations (eg, tetramethyl group). Anidium ion).
Examples of the ionic hydrophilic group in the salt state include lithium sulfonate, potassium carboxylate, and tetramethylammonium chloride.

  Among the above substituents, those having a hydrogen atom may be substituted with the above substituent. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

Next, the details of the step (b) according to the present invention will be described.
In the step (b), the diazonium compound adjustment liquid obtained in the step (a) and the compound represented by the general formula (1) are mixed, and the diazonium compound in the diazonium compound adjustment liquid obtained in the step (a) In this step, the compound represented by the general formula (1) is coupled. (A) Although there is no limitation in the mixing method of the diazonium compound adjustment liquid obtained at the process and the compound represented by General formula (1), In the mixture of the compound represented by General formula (1) and a solvent It is preferable to add the diazonium compound adjusting liquid obtained in the step (a).

The amount of the diazonium compound in the diazonium compound adjustment liquid obtained in the step (a) with respect to the compound represented by the general formula (1) used in the step (b) is the coupling of the compound represented by the general formula (1). It is preferably 1 to 5 equivalents relative to the position, more preferably 1.05 to 3 equivalents relative to the coupling position, and even more preferably 1.1 to 2 equivalents relative to the coupling position. In order to achieve coupling at all coupling positions in the compound represented by the general formula (1) to be used, 1 equivalent is required for the diazonium moiety, and a diazonium compound is used in a large amount at 5 equivalents or more. This is uneconomical.

Although it does not specifically limit as a solvent of the compound represented by General formula (1) used for (b) process, An alcohol solvent and an organic acid solvent are mentioned. Moreover, the mixed solvent containing an alcohol solvent and the mixed solvent containing an organic acid can also be used. Examples of the alcohol solvent include methanol, ethanol, isopropanol, pentanol, heptanol, octanol, cyclohexanol, benzyl alcohol, phenethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, and anise alcohol. Also not only mono-, but also oligo- (especially di- and tri-) and poly-C ₂ -C ₄ -alkylene glycols (in short “glycols”) and their mono-C ₁ -C ₈ -alkyl- and Also suitable are monoaryl ethers (in short, “glycol monoethers”). Also advantageous are compounds based on ethylene. Examples include ethylene glycol, 1,2- and 1,3-propylene glycol, diethylene glycol, butylene glycol, di-, tri- and tetraethylene glycol, di-, tri- and tetrapropylene glycol, polyethylene- and polypropylene glycol, ethylene Glycol monomethyl-, -monoethyl-, -monopropyl-, -monobutyl- and -monohexyl ether and propylene glycol monomethyl-, -monoethyl-, -monopropyl-, -monobutyl- and -monohexyl ether, di-, tri- And tetraethylene glycol monomethyl-, -monoethyl- and -monobutyl ether and di-, tri- and tetrapropylene glycol monomethyl-, -monoethyl- and -monobutyl ether and ethyl - and it includes propylene glycol monophenyl ether. Most preferably, methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol is used. These mixed solvents are also advantageous.

  The preferable amount of the solvent added to the compound represented by the general formula (1) is preferably 0.5 to 200 times, more preferably 1 to 100 times, and still more preferably 1 to 50 times in terms of mass ratio. As the addition amount of a preferable solvent amount with respect to the compound represented by the general formula (1), when the mass ratio is 0.5 times or less, stirring in the machine for producing the compound represented by the general formula (1) and the solvent becomes difficult. The desired reaction does not proceed. Moreover, it becomes uneconomical at 200 times or more.

  Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, and methanesulfonic acid, preferably acetic acid, propionic acid, and methanesulfonic acid, and more preferably acetic acid and propionic acid.

  Mixed solvents including alcohol solvents include acetonitrile, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, propylene carbonate, N-methyl-2-pyrrolidone, and N-vinyl-2-pyrrolidone. , N, N-diethyldodecanamide). A mixed solvent of the organic acid and alcohol solvent shown above is also suitable.

Further, the mixture of the compound represented by the general formula (1) and the solvent may contain a base. Examples of the base include triethylamine, tributylamine, diisopropylethylamine, pyridine, dimethylaminopyridine, DBU (1,8-diazabicyclo [5.4.0] -7-undecene and other organic bases, lithium carbonate, sodium carbonate, potassium carbonate, Inorganic bases such as sodium bicarbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. Other salts of organic acid and strong base include lithium acetate, potassium acetate, sodium oxalate, disodium ethylenediaminetetraacetate And so on.
When adding a base, the addition time of a base is not specifically limited. The diazonium compound adjusting solution in the step (a) may be mixed with the mixed solution of the compound represented by the general formula (1), the base, and the solvent, to the mixed solution of the compound represented by the general formula (1) and the solvent. You may mix the diazonium compound adjustment liquid of a process and a base alternately.

The preferable pH of the mixed solution in the step (b) is preferably 12 or less, more preferably 10 or less, and still more preferably 9 or less. When the pH of the mixed solution in the step (b) is 12 or more, the diazonium compound induced in the step (a) is decomposed, and there is a concern about the progress of a desired reaction.

In the step (b), the mixing temperature of the diazonium compound adjusting solution in the step (a) and the compound represented by the general formula (1) is preferably 20 ° C. or lower, more preferably 15 ° C. or lower. Preferably, it is desirable to carry out at 12 ° C. or lower. Above 20 ° C., there is a concern about the decomposition of the diazonium compound induced in the step (a). Moreover, a normal stirrer is used for mixing, and there is no limitation in particular. Although depending on the production equipment, the preferred stirring speed is preferably 30 to 300 rpm, more preferably 40 to 200 prm, and still more preferably 50 to 200 rpm. When the stirring speed is 30 rpm or less, the stirring efficiency of the mixed solution deteriorates and there is a concern about the progress of a desired reaction. The stirring time in the step (b) is preferably 0.3 to 10 hours, more preferably 0.5 to 5 hours, and further preferably 1 to 3 hours. If it is 0.3 hours or less, it is difficult to induce the azo compound completely, and if it is 10 hours or more, the azo compound may be decomposed by the acid used in the step (a).
(B) Since the reaction liquid after completion | finish of a process becomes strongly acidic, when it heats as it is, decomposition | disassembly of the produced | generated azo compound will advance notably. Therefore, it is preferable to neutralize a part of the strong acid in the reaction solution.

Next, the compound represented by the general formula (1) according to the present invention will be described in detail.

Each X independently represents a hydrogen atom or a substituent, and this substituent may further have a substituent.
Y represents —OR ¹ , —NR ² R ³ , —SR ⁴ , and R ¹ represents a hydrogen atom, an alkali metal ion, an organic cation, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. R ^{2 to} R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. These groups may further have a substituent.
Z represents —OM, M represents a hydrogen atom or a metal ion, represents —NR ⁵ R ⁶ , and R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl A group, a heterocyclic group, an alkyl or arylcarbonyl group, an alkyl or arylsulfonyl group; These groups may further have a substituent.
G represents a hydrogen atom or a halogen atom.
Q represents an atomic group constituting a nitrogen-containing heterocyclic ring together with a carbon atom directly connected to pyrazole.
n, s, and t represent integers satisfying the relationships of 1 ≦ n ≦ 3, 0 ≦ s ≦ 2, 0 ≦ t ≦ 1, and n + s + t = 3.

  Details of the general formula (1) will be described below.

  X in the said General formula (1) shows a hydrogen atom or a substituent each independently. Preferred substituents are halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aralkyl groups, aryl groups, heterocyclic groups, cyano groups, carboxyl groups, carbamoyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyl groups, hydroxy groups Substituted with an alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, alkyl group, aryl group or heterocyclic group Amino group, acylamino group, sulfamoylamino group, alkoxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, thio group, alkyl or arylthio group, Represents a thio group, a carbamoylthio group, a heterocyclic thio group, an alkoxycarbonylthio group, an aryloxycarbonylthio group, an alkyl or arylsulfinyl group, a sulfamoyl group, an ionic hydrophilic group, or an amide group, more preferably a halogen atom, Alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, Carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, alkyl group, aryl group or amino group substituted with heterocyclic group, acylamino group, sulfamoylamino , Alkoxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, thio group, alkyl or arylthio group, acylthio group, carbamoylthio group, heterocyclic thio group, alkoxycarbonylthio group, aryloxycarbonylthio group, Represents an ionic hydrophilic group or an amide group, more preferably a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, amino Represents an amino group, a thio group, an alkyl or arylthio group, a heterocyclic thio group, or an ionic hydrophilic group substituted with a group, an alkyl group, an aryl group or a heterocyclic group. Among them, preferred substituents include alkyl groups having 1 to 8 carbon atoms and aryl groups having 6 to 12 carbon atoms, and isopropyl groups, sec-butyl groups, and tert-butyl groups are most preferable. Each group may further have a substituent.

Q represents an atomic group constituting a heterocyclic ring containing at least one nitrogen atom (nitrogen-containing heterocyclic ring), more preferably an atom constituting a 5-membered or 6-membered heterocyclic ring containing at least one nitrogen atom. Represents an atomic group constituting a 6-membered heterocyclic ring containing at least one nitrogen atom.
The nitrogen-containing heterocycle composed of a carbon atom directly connected to Q and pyrazole is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. Preferred examples of the heterocyclic ring include imidazole, benzimidazole, pyrazole, benzopyrazole, triazole, thiazole, benzothiazole, isothiazole, benzoisothiazole, oxazole, benzoxazole, thiadiazole, pyrrole, benzopyrrole, indole, isoxazole, benzo Examples include isoxazole, pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, pyrazine, cinnoline, phthalazine, quinazoline, quinoxaline, and triazine. More preferred are pyridine, pyridazine, pyrimidine, pyrazine, and triazine, most preferred are pyridazine, pyrimidine, pyrazine, and triazine, and most preferred is triazine.

Y represents —OR ¹ , —NR ² R ³ , or —SR ⁴ , preferably —OR ¹ or —NR ² R ³ , and more preferably —OR ¹ .

R ^{1 in} Y represents a hydrogen atom, an alkali metal ion, an organic cation, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group, preferably a hydrogen atom, an alkali metal ion, or an organic cation. , An alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkali metal ion.

R ^{2 to} R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group, more preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Are more preferable, and a hydrogen atom, an alkyl group, or a heterocyclic group is more preferable.

The alkali metal ion represented by R ¹ is, for example, lithium ion, sodium ion, or potassium ion, and more preferably lithium ion or potassium ion.

The organic cation represented by R ¹ is, for example, an ammonium ion or a tetramethylguanidinium ion, and more preferably an ammonium ion.

Specific examples of the alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, and heterocyclic group represented by R ^{1 to} R ⁴ and examples of the substituent that may be included are the substituents that the aforementioned amino compound may have. And preferred examples are also the same.

The groups R ^{1 to} R ^{4 in} Y may further have a substituent. The details of the substituent are synonymous with those of the above-mentioned amino compound and preferred examples are also the same.

Z represents -OM, a ^-NR 5 ^{R 6,} preferred groups are ^-NR 5 ^{R 6.}

  G represents a hydrogen atom or a halogen atom, preferably a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom or a chlorine atom, and still more preferably a chlorine atom.

R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkyl or arylcarbonyl group, or an alkyl or arylsulfonyl group. Preferably, it represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or an alkyl or arylcarbonyl group. More preferably, it represents a hydrogen atom, an alkyl group, an aryl group, or an alkyl or arylcarbonyl group. Most preferably, it is a hydrogen atom.

Specific examples of the alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, and heterocyclic group represented by R ⁵ and R ⁶ are the same as the substituents R ^{1 to} R ^{4 in} Y, and are preferred examples. There is the same.

The alkyl or arylcarbonyl group represented by R ⁵ and R ⁶ includes an alkyl or arylcarbonyl group having a substituent. As the alkylcarbonyl group, an alkylcarbonyl group having 2 to 6 carbon atoms when a substituent is removed is preferable. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group. Examples of the alkylcarbonyl group include an acyl group, an ethylcarbonyl group, a trifluoromethyl group, and a pivaloyl group. The arylcarbonyl group is preferably an arylcarbonyl group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, a nitro group, a cyano group, and an ionic hydrophilic group. Examples of the arylcarbonyl group include a benzoyl group, a p-chlorobenzoyl group, and an m-carboxyphenylcarbonyl group.

The alkyl or arylsulfonyl group represented by R ⁵ and R ^{6 includes} an alkyl or arylsulfonyl group having a substituent and an unsubstituted alkyl or arylsulfonyl group. The alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 5 carbon atoms when a substituent is removed. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group. Examples of the alkylsulfonyl group include a mesyl group, an ethylsulfonyl group, and a trifluoromethylsulfonyl group. Moreover, as an arylsulfonyl group, a C6-C11 arylsulfonyl group when a substituent is remove | excluded is preferable. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, a nitro group, a cyano group, and an ionic hydrophilic group. Examples of the arylsulfonyl group include a phenylsulfonyl group, a p-chlorosulfonyl group, and an m-carboxyphenylsulfonyl group.

  The substituent that each substituent may have has the same meaning as the substituent that the amino compound may have, and preferred examples thereof are also the same.

  n, s, and t represent the number of substitutions of pyrazole, substituent Y, and substituent G, respectively. n represents an integer of 1 or more, and in the production method of the present invention, the number of substitutions is preferably 1 to 3 in terms of production time and yield, more preferably 2 or 3, and most preferably 2. . s represents an integer of 0 or more, preferably an integer of 1 or more, more preferably 1 or 2, and particularly preferably 1. t represents an integer of 0 or more, preferably represents an integer of 0 to 4, more preferably 0 or 1.

  Moreover, the compound represented by General formula (1) may form a dimer with L (divalent coupling group).

The divalent linking group represented by L includes an oxy group —O—, a thio group —S—, a carbonyl group —CO—, a sulfonyl group —SO ₂ —, an imino group —NH—, a methylene group —CH ₂ —, A phenylene group -Ph-, a heterocyclic group, and a group formed by combining these groups. Examples of the group formed by a combination of linking groups include urea, triazine, 1,3-diaminopropane, and 1,4-phenylene. Examples include diamines.

In summary, the general formula (1) of the present invention is preferably composed of the following combinations (a) to (h).
(A) X is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, more preferably an isopropyl group, a sec-butyl group, or a tert-butyl group, and tert-butyl. The group is most preferred.
(B) Z represents —OM or —NR ⁵ R ⁶ , preferably —NR ⁵ R ⁶ . R ⁵ and R ⁶ are each independently preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or an alkyl or arylcarbonyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, or an alkyl group. Or an arylcarbonyl group, and most preferably a hydrogen atom.
(C) Q represents an atomic group constituting a heterocyclic ring containing at least one nitrogen atom (nitrogen-containing heterocyclic ring), more preferably a 5-membered or 6-membered heterocyclic ring containing at least one nitrogen atom. It is an atomic group constituting, more preferably an atomic group constituting a 6-membered heterocyclic ring containing at least one nitrogen atom. The nitrogen-containing heterocyclic ring composed of Q and the carbon atom directly connected to pyrazole is pyridine, pyridazine, pyrimidine, pyrazine, or triazine, most preferably pyridazine, pyrimidine, pyrazine, or triazine, most preferably Triazine.
(2) Y represents —OR ¹ , —NR ² R ³ , or —SR ⁴ , preferably —OR ¹ or —NR ² R ³ , and more preferably —OR ¹ . Further, among R ¹ , a hydrogen atom, an alkali metal ion, an organic cation, an alkyl group, or an aryl group is preferable, and a hydrogen atom or an alkali metal ion is more preferable. Among alkali metal ions, lithium ion, sodium ion, or potassium ion is more preferable, and lithium ion or potassium ion is most preferable.
(E) G represents a hydrogen atom or a halogen atom, preferably a halogen atom. Among the halogen atoms, a fluorine atom or a chlorine atom is more preferable, and a chlorine atom is more preferable.
(F) n represents an integer of 1 to 3, more preferably 2 or 3, and most preferably 2.
(G) s represents 0, 1, or 2, more preferably 1 or 2, and most preferably 1.
(H) t represents an integer of 0 or 1, more preferably 0.
The compound represented by the general formula (1) is preferably a compound in which at least one of various substituents is the above preferred group, and more preferably a compound in which more various substituents are the above preferred group. Most preferred are compounds in which all substituents are the preferred groups described above.

  Among the compounds represented by the general formula (1), a compound represented by the following general formula (2) is more preferable.

In the general formula (2):
Each X independently represents a hydrogen atom or a substituent, and this substituent may further have a substituent.
Y represents —OR ¹ , —NR ² R ³ , or —SR ⁴ , and R ¹ represents a hydrogen atom, an alkali metal ion, an organic cation, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic ring. R ^{2 to} R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. These groups may further have a substituent.
Z represents —OM or —NR ⁵ R ⁶ . However, M represents a hydrogen atom or a metal ion, and R ⁵ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, alkyl or arylcarbonyl group, acyl A group, or an alkyl or arylsulfonyl group. These groups may further have a substituent.
G represents a hydrogen atom or a halogen atom.
n, s, and t represent integers satisfying the relationships of 1 ≦ n ≦ 3, 0 ≦ s ≦ 2, 0 ≦ t ≦ 1, and n + s + t = 3.

  X, Y, and Z are synonymous with X, Y, and Z described in the description of the general formula (1), and preferred examples are also the same.

  Moreover, the compound represented by General formula (2) may form a dimer with L (divalent coupling group).

The divalent linking group represented by L includes an oxy group —O—, a thio group —S—, a carbonyl group —CO—, a sulfonyl group —SO ₂ —, an imino group —NH—, a methylene group —CH ₂ —, A phenylene group -Ph-, a heterocyclic group, and a group formed by combining these groups. Examples of the group formed by a combination of linking groups include urea, triazine, 1,3-diaminopropane, and 1,4-phenylene. Diamine.

In summary, the general formula (2) of the present invention is preferably composed of the following combinations (a) to (g).
(A) X is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, more preferably an isopropyl group, a sec-butyl group, or a tert-butyl group, A butyl group is most preferred.
(B) Z represents —OM or —NR ⁵ R ⁶ , preferably —NR ⁵ R ⁶ . R ⁵ and R ⁶ preferably represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or an alkyl or arylcarbonyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, or Represents an alkyl or arylcarbonyl group, and most preferably a hydrogen atom.
(C) Y represents —OR ¹ , —NR ² R ³ , or —SR ⁴ , preferably —OR ¹ or —NR ² R ³ , and more preferably —OR ¹ . Further, among R ¹ , a hydrogen atom, an alkali metal ion, an organic cation, an alkyl group, or an aryl group is preferable, and a hydrogen atom or an alkali metal ion is more preferable. Among alkali metal ions, lithium ion, sodium ion, or potassium ion is more preferable, and lithium ion or potassium ion is most preferable.
(D) G represents a hydrogen atom or a halogen atom, preferably a halogen atom. Among the halogen atoms, a fluorine atom or a chlorine atom is more preferable, and a chlorine atom is more preferable.
(E) n represents an integer of 1 to 3, more preferably 2 or 3, and most preferably 2.
(F) s represents 0, 1, or 2, more preferably 1 or 2, and most preferably 1.
(G) t represents an integer of 0 or 1, more preferably 0.
The compound represented by the general formula (2) is preferably a compound in which at least one of various substituents is the above preferred group, more preferably a compound in which more of the substituents are the above preferred group, Most preferred are compounds in which the above substituents are the above preferred groups.

  Among the compounds represented by the general formula (2), a compound represented by the following general formula (3) is more preferable.

In the general formula (3), X ¹ and X ² , Z ¹ and Z ² are each independently synonymous with X and Z, and Y is synonymous with Y.

  Hereinafter, the compound represented by the general formula (3) will be described in detail.

  X, Y, and Z are synonymous with X, Y, and Z described in the description of the general formula (1), and preferred substituents are also the same.

In summary, the general formula (3) of the present invention is preferably composed of the following combinations (a) to (c).
(A) X ¹ and X ² are each independently preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and is preferably an isopropyl group, sec-butyl group, or tert-butyl. Group is more preferred, and tert-butyl group is most preferred.
(B) Z ¹ and Z ² each independently represent —OM and —NR ⁵ R ⁶ , preferably —NR ⁵ R ⁶ . R ⁵ and R ⁶ preferably represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or an alkyl or arylcarbonyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, or Represents an alkyl or arylcarbonyl group, and most preferably a hydrogen atom.
(C) Y represents —OR ¹ , —NR ² R ³ , or —SR ⁴ , preferably —OR ¹ or —NR ² R ³ , and more preferably —OR ¹ . Further, among R ¹ , a hydrogen atom, an alkali metal ion, an organic cation, an alkyl group, or an aryl group is preferable, and a hydrogen atom or an alkali metal ion is more preferable. Among alkali metal ions, lithium ion, sodium ion, or potassium ion is more preferable, and lithium ion or potassium ion is most preferable.
The compound represented by the general formula (3) is preferably a compound in which at least one of various substituents is the above preferred group, more preferably a compound in which more of the substituents are the above preferred group, Most preferred are compounds in which the above substituents are the above preferred groups.

  The production method of the present invention is most preferably used for a production method of an azo compound represented by the following general formula (5).

In the general formula (5), Q ¹ and Q ² are each independently an aromatic hydrocarbon ring group, a non-aromatic hydrocarbon ring group, an aromatic heterocyclic group or a non-aromatic hetero ring which may have a substituent. Represents a cyclic group, and the substituent may further have a substituent. X ¹ and X ² are each independently synonymous with X, Z ¹ and Z ² are each independently synonymous with Z, Y represents —OR ¹ , and R ¹ represents a hydrogen atom or a metal ion. .
The detailed description of the substituent is synonymous with the substituent that the amino compound may have, and the preferred examples are also synonymous.

Q ¹ and Q ² each independently represents an aromatic hydrocarbon ring group, a non-aromatic hydrocarbon ring group, an aromatic heterocyclic group or a non-aromatic heterocyclic group which may have a substituent, And fused rings are also included. Of these, a heterocyclic group is preferable, and a nitrogen-containing 5- to 7-membered heterocyclic group is more preferable. Preferred examples Q ¹ and Q ² below, and more preferred examples, more preferred is an example, substitution position and binds to the azo group of Q ¹ and Q ^2, the substituent that may have for Q ¹ and Q ² And the substitution position is not limited. Preferable examples of Q ¹ and Q ² include phenyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, benzopyrazolyl group, triazolyl group, thiazolyl group, benzothiazolyl group, isothiazolyl group, benzoisothiazolyl group, oxazolyl group, benzoxayl group Zolyl, thiadiazolyl, pyrrolyl, benzopyrrolyl, indolyl, isoxazolyl, benzoisoxazolyl, thiophenyl, benzothiophenyl, furanyl, benzofuranyl, pyridinyl, quinolinyl, isoquinolinyl, pyridazinyl Group, pyrimidinyl group, pyrazinyl group, cinnolinyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, or triazinyl group. More preferred examples of Q ¹ and Q ² are pyridinyl group, pyrimidinyl group, pyridazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, or thiadiazolyl group, Preferred examples are a pyrazolyl group, a thiazolyl group, an isothiazolyl group, or a thiadiazolyl group. Particularly preferred is a pyrazolyl group. Among them, the substituent of the pyrazolyl group is preferably a cyano group, —SO ₂ CH ₃ or —SO ₂ Ph, and most preferably the substituent of the pyrazolyl group is a cyano group.

In summary, the general formula (5) of the present invention is preferably composed of the following combinations (a) to (d).
(A) X ¹ and X ² are each independently preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and is preferably an isopropyl group, sec-butyl group, or tert-butyl. Group is more preferred, and tert-butyl group is most preferred.
(B) Z ¹ and Z ² each independently represent —OM and —NR ⁵ R ⁶ , preferably —NR ⁵ R ⁶ . R ⁵ and R ⁶ preferably represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or an alkyl or arylcarbonyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, or Represents an alkyl or arylcarbonyl group, and most preferably a hydrogen atom.
(C) Y represents —OR ¹ , and R ¹ represents a hydrogen atom or a metal ion. More preferred are a hydrogen atom and an alkali metal ion, and still more preferred is an alkali metal ion. Among alkali metal ions, lithium ion, sodium ion, or potassium ion is more preferable, and lithium ion or potassium ion is most preferable.
(D) Q ¹ and Q ² are each independently a pyridinyl group, pyrimidinyl group, pyridazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, or thiadiazolyl group And a more preferred example is a pyrazolyl group, a thiazolyl group, an isothiazolyl group, or a thiadiazolyl group, particularly preferably a pyrazolyl group. Among them, the substituent of the pyrazolyl group is preferably a cyano group, —SO ₂ CH ₃ or —SO ₂ Ph, and most preferably the substituent of the pyrazolyl group is a cyano group.
The compound represented by the general formula (5) is preferably a compound in which at least one of various substituents is the above preferred group, more preferably a compound in which more of the substituents are the above preferred group, Most preferred are compounds in which the above substituents are the above preferred groups.

  Specific examples of the compound represented by the general formula (5) are given below, but the present invention is not limited thereto.

Next, the details of the step (c) according to the present invention will be described.
By performing the step (c) of stirring the mixed solution obtained in the step (b) while heating, the produced azo compound can be taken out in a short time with a high yield. Here, “while heating” means keeping the temperature of the mixed solution at room temperature or higher.

As a heating condition in the step (c), the temperature of the mixed solution is preferably 40 to 100 ° C, more preferably 50 to 80 ° C, and most preferably 50 to 75 ° C. When the temperature of the mixed liquid is 40 ° C. or lower, the filterability is insufficient, and when the temperature of the mixed liquid is 100 ° C. or higher, the precipitated azo compound is dissolved, and the decomposition of the azo compound is promoted to yield. Decreases. There is no particular limitation on the heating rate.

The time of stirring while heating in the step (c) is preferably 0.5 hours or more, more preferably 0.5 to 4 hours, and most preferably 1 to 2 hours. If the heating time is too short, the effect of improving the filterability is low. On the other hand, if the heating time is too long, the decomposition of the azo compound is accelerated as described above, resulting in a decrease in yield. Moreover, a normal stirrer is used for stirring, and there is no restriction in particular. Although depending on the production equipment, the preferred stirring speed is preferably 30 to 300 rpm, more preferably 40 to 200 prm, and still more preferably 50 to 200 rpm. When the stirring speed is 30 rpm or less, the stirring efficiency of the mixed solution deteriorates and there is a concern about the progress of a desired reaction.

(B) Since the mixed liquid after the process is strongly acidic, the decomposition of the produced azo compound may be remarkably progressed only by heating and stirring as it is. For this reason, it is preferable to stir while heating, after neutralizing a part of strong acid of a liquid mixture with a base. The base used includes triethylamine, sodium methoxide, or ammonia as the organic base. The inorganic base is preferably an alkali metal hydroxide. These bases may be used alone or in a state mixed with a medium. The medium includes water, methanol, ethanol, isopropanol, or ethylene glycol. As an example, an ammonia aqueous solution or an organic solution is preferable, triethylamine, a methanol solution of sodium methoxide, a methanol solution or aqueous solution of potassium hydroxide, an ammonia methanol solution or an aqueous solution is more preferable, and a methanol solution of potassium hydroxide is most preferable. A preferable addition amount of the base is preferably an amount capable of completely neutralizing the acid used in the step (a), more preferably, in the step (c), the mixed solution pH is in the range of 0 to 7, more preferably, The pH is 0 to 5, and the pH is most preferably 0 to 3.

(C) 0-10 are preferable, as for the pH of the solution at the time of the heating in a process, 0-9 are more preferable, and 0-7 are the most preferable.

In summary, the production method of the azo compound of the present invention is preferably a production method comprising the following combinations (a) to (h).
(I) As the acid used in the production method of the present invention, inorganic acids and organic acids can be used. Examples of inorganic acids include hydrochloric acid, phosphoric acid, and sulfuric acid, preferably phosphoric acid and sulfuric acid, and more preferably sulfuric acid. It is. Examples of the organic acid include formic acid, acetic acid, propionic acid, and methanesulfonic acid, preferably acetic acid, propionic acid, and methanesulfonic acid, and more preferably acetic acid and methanesulfonic acid. These acids may be used alone or in combination. Of these, the most preferred is a mixed acid of sulfuric acid and acetic acid.
(B) The amino compound used in the production method of the present invention means an aromatic amino compound which may have a substituent, and includes a single ring and a condensed ring. Of these, a heterocyclic amino group is preferable, and a nitrogen-containing 5- to 7-membered heterocyclic amino compound is more preferable. Most preferred are 5-aminopyrazole derivatives and salts thereof, and particularly preferred are 5-aminopyrazole derivatives represented by the general formula (4) and salts thereof. More preferably, the substituent R ¹² in the general formula (4) is a Hammett substituent constant σp value of 0.20 or more, and the preferable substituent R ¹² is a cyano group, a carbamoyl group, an alkoxycarbonyl group. An alkylsulfonyl group and a phenylsulfonyl group, and most preferably a cyano group.
(C) The mass ratio of the acid to the amino compound is 1 to 100 times, more preferably 2 to 50 times, and still more preferably 3 to 25 times.
(D) The amount of the diazotizing agent relative to the amino compound is 1.0 to 20 times in molar ratio, more preferably 1.0 to 10 times, and even more preferably 1.0 to 5 times.
(E) The mixing of the diazotizing agent, the acid and the amino compound is preferably performed at 20 ° C. or less, more preferably at 15 ° C. or less, and further preferably at 12 ° C. or less. .
(F) As the diazotizing agent, nitrosylsulfuric acid or sodium nitrite is preferable, and nitrosylsulfuric acid is most preferable.
(G) Among the compounds of the general formula (1) used in the step (b) of the production method of the present invention, the compound represented by the general formula (2) is preferable, and n is most preferably 1 to 3 among 1 to 3. preferable. Among the compounds of the general formula (2), the compound represented by the general formula (3) is preferable.
(H) In the production method of the present invention, it is preferable to introduce a step (c) in which heating and stirring are performed after the step (b).

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Synthesis of azo compound by steps (a) and (b)>
[Example 1]

Synthesis scheme 1 of azo compound 1

  (Synthesis of Compound 1) 25.5 g of sodium hydrogen carbonate and 150 mL of ion-exchanged water were heated to 40 ° C., 25.0 g of cyanuric chloride was added in 5 portions every 10 minutes, and the mixture was stirred for 1 hour. The solution was added dropwise to a mixed solution (8 ° C.) of 52.8 mL of hydrazine and 47 mL of ion exchange water so that the internal temperature did not exceed 10 ° C. The internal temperature was raised to 50 ° C. and stirred for 30 minutes. The precipitated crystals were filtered to obtain 23.4 g of white crystals. The yield was 94.7%.

  35.0 g of the above white crystals were suspended in 420 mL of ethylene glycol and stirred at an internal temperature of 50 ° C. Concentrated hydrochloric acid (59 mL) was added, followed by 60.1 g of pivaloyl acetonitrile, and the mixture was stirred at 50 ° C. for 10 hours. Concentrated hydrochloric acid (95 mL) and methanol (145 mL) were added, and the mixture was further stirred for 8 hours. After cooling to room temperature, the precipitated crystals were separated by filtration to obtain 81.6 g of Compound 1. The yield was 94.2%.

(Synthesis of Compound A) 36.2 g of 5-aminoisophthalic acid was suspended and dispersed in 200 mL of ion-exchanged water, and 36.8 mL of 95% sulfuric acid was added dropwise thereto. The mixture was stirred at an internal temperature of 25 ° C. for 20 minutes and cooled until the internal temperature reached 2 ° C. Thereto, 21.2 mL of an aqueous solution of 13.9 g of sodium nitrite was added with an internal temperature of 5 ° C. as the upper limit. Subsequently, the mixture was stirred at an internal temperature of 10 ° C. for 1 hour (reaction solution A). The reaction solution A was added to 130 mL (internal temperature 20 ° C.) of an aqueous solution of 75.6 g of sodium sulfite separately prepared, and the temperature was raised until the internal temperature reached 70 ° C., followed by stirring at this temperature for 1.5 hours. Thereafter, 33.8 mL of 95% sulfuric acid was added dropwise at an internal temperature of 75 ° C. or lower, and the mixture was stirred at an internal temperature of 85 ° C. for 3 hours. After cooling to an internal temperature of 25 ° C., the precipitated white crystals were subjected to suction filtration, washed with 300 mL of ion exchange water and then with 200 mL of isopropanol, and dried at 75 ° C. Yield 50.6 g (Yield 103.1%). 15.5 g of this white crystal was suspended in 49.4 g of methanol, and then triethylamine was added until the white crystal was completely dissolved (18.3 g was used). 8.1 g of ethoxymethylidenemalononitrile was added at an internal temperature of 30 ° C., and the temperature was raised to an internal temperature of 40 ° C., followed by stirring for 1 hour. Further, after raising the internal temperature to 50 ° C., 5.1 g of hydrochloric acid was added dropwise, and the temperature was raised to the reflux temperature. After stirring for 1 hour, the internal temperature was cooled to 25 ° C., and the precipitated pale yellow crystals were suction filtered. After washing with 33.2 g of isopropanol, it was dried at 75 ° C. to obtain Compound A. Yield 17.7 g (yield 70.9%).
[Synthesis 3]

(Synthesis of Azo Compound 1) After stirring 23.8 g of 95% sulfuric acid at an internal temperature of 10 ° C., 61.1 g of acetic acid was added to keep the internal temperature at 7 ° C. 6.4 mL of 40% nitrosylsulfuric acid (manufactured by Aldrich) was added dropwise thereto. Further, 12.9 g of Compound A was added in portions and stirred at an internal temperature of 10 ° C. for 1 hour. To this reaction solution, 0.7 g of urea was added, and stirring was further continued for 1 hour (reaction solution B). Reaction solution B was added dropwise at an internal temperature of 10 ° C. or lower to 148.2 g of methanol solution (internal temperature 4 ° C.) of 7.5 g of Compound 1 separately prepared. After dropping, the mixture was stirred at an internal temperature of 10 ° C. for 15 minutes, and the temperature was raised to an internal temperature of 20 ° C. After stirring at this temperature for 1.5 hours, the precipitated yellow crystals were suction filtered. After washing with 126.4 g of methanol, all the crystals were suspended in 148.2 g of methanol. After raising the temperature to the reflux temperature, the mixture was refluxed for 1 hour and cooled to an internal temperature of 30 ° C. The yellow crystals were subjected to suction filtration, and then washed with 63.2 g of methanol, followed by 160 g of ion-exchanged water, and subsequently with 63.2 g of methanol. The crystals were dried at 75 ° C. Yield 13.8 g (Yield 87.0%). 10.0 g of this yellow crystal was suspended and dispersed in 47 g of ion-exchanged water, and 11 mL of a 5 mol / L potassium hydroxide aqueous solution was added dropwise at room temperature to adjust the pH to 7.5. This solution was heated to an internal temperature of 50 ° C., 223 mL of isopropanol was added, and the internal temperature was cooled to 30 ° C. The precipitated yellow crystals were suction filtered and washed with 223 mL of isopropanol. After drying at 75 ° C., 11.6 g of azo compound 1 was obtained (yield 96.4%). λmax: 436.2 nm (H ₂ O), ε: 33800
[Example 2]

Synthesis scheme 2 of azo compound 16

  (Synthesis of Compound B) 4-Nitrophthalonitrile (Tokyo Chemicals) 251.3 g was dissolved in 2500 mL of dimethyl sulfoxide, and then 2-amino-5-mercapto-1,3,4-thiadiazole (Wako Pure Chemicals) 290. 0 g was added followed by 220.7 g potassium carbonate. After raising the internal temperature to 40 ° C., the mixture was stirred for 3.5 hours. This reaction solution was transferred to 15000 mL of ion-exchanged water, and the precipitated crystals were separated by filtration. Subsequently, the crystals were suspended and dispersed in a mixed solvent of 900 mL of isopropanol and 300 mL of methanol and stirred at room temperature for 1.5 hours. The crystals were separated by filtration, washed with 500 mL of isopropanol and dried. Yield 357.4 g (95% yield).

100.0 g of this crystal was added in portions to a mixed solution of 86.7 mL of 95% sulfuric acid having an internal temperature of 75 ° C and 34.7 mL of ion-exchanged water, and the temperature was raised to 120 ° C. After stirring for 1 hour, the mixture was cooled to room temperature and 200 mL of acetone was added and suspended and dispersed. The crystals separated by filtration were washed with acetone and dried to obtain 179.35 g of Compound B (yield 117.5%).
[Synthesis 5]

(Synthesis of Azo Compound 16) 32.7 g of Compound B was completely dissolved in a mixed solution of 71.4 mL of methanesulfonic acid, 85.6 mL of acetic acid, and 128.4 mL of propionic acid at room temperature. After cooling the internal temperature to 4 ° C., 16 mL of an aqueous solution of 8.0 g of sodium nitrite was added dropwise, and the mixture was stirred at an internal temperature of 5 ° C. or lower for 1.5 hours (Reaction Solution C). Reaction solution C was added dropwise to a separately prepared Compound 1 22.2 g ethylene glycol 440 mL / methanol 220 mL solution (internal temperature −8 ° C. or lower) over 0.5 hour. This dispersion was transferred to 4200 mL of acetonitrile, stirring was stopped, and the precipitate was allowed to settle. After removing the supernatant, 2500 mL of acetonitrile was added to the residue, and the precipitate was allowed to settle after stirring for 15 minutes. After removing the supernatant, the precipitate was filtered and dispersed in 900 mL of ion-exchanged water. After stirring at room temperature for 2 hours, it was filtered and washed with ion exchange water. After drying, 43.9 g of yellow crystals were obtained (yield 88.0%). λmax: 451.7 nm (H ₂ O), ε: 59400
[Example 3]

Synthesis scheme 3 of azo compound 20

(Synthesis of Compound C) 800 g of dimethyl sodium 5-sulfoisophthalate was dissolved in 800 mL of dimethylformamide, 2400 mL of acetonitrile was added, and 800 mL of phosphorus oxychloride was added dropwise. The mixture was stirred at an internal temperature of 60 ° C. for 3.5 hours and then cooled to 45 ° C. The reaction solution was transferred to 12 L of ice water and stirred for 1 hour. The crystals separated by filtration were washed with 12 L of ion-exchanged water, and then the crystals were air-dried (yield 758.3 g, yield 95.9%). 213.4 g of this crystal was added to 2500 mL of a methanol solution of 100.0 g of m-aminobenzoic acid, and the internal temperature was kept at 10 ° C. After adding 59.0 mL of pyridine thereto, the temperature was raised to an internal temperature of 23 ° C. After stirring at this temperature for 1 hour, the precipitated crystals were separated by filtration and washed twice with 2500 mL of ion-exchanged water. After drying at 70 ° C., 246.1 g of white crystals (yield 85.7%) was obtained. 196.7 g of this white crystal was added to 700 mL of ethyl acetate and heated to an internal temperature of 50 ° C. After 47.2 mL of thionyl chloride was added dropwise thereto, the mixture was stirred at an internal temperature of 60 ° C. for 1 hour. Subsequently, the temperature was raised and refluxed for 1 hour. After cooling to an internal temperature of 20 ° C., the solution was transferred to 600 mL of acetonitrile prepared separately at an internal temperature of 5 ° C. To this reaction solution, 91.1 g of thiosemicarbazide was added and stirred at an internal temperature of 7 ° C. for 0.5 hour. At this temperature, 800 mL of cold water was poured, and the mixture was warmed to room temperature and stirred for 1 hour. The precipitated crystals were separated by filtration and washed twice with 1000 mL of ion-exchanged water and then with 250 mL of cold acetonitrile. After drying the crystals, 223.0 g (yield 95.6%) of compound C was obtained.
[Synthesis 7]

  (Synthesis of Azo Compound 20) 137.8 g of Compound C was added in portions to 275 mL of 95% sulfuric acid cooled to 10 ° C., and the temperature was raised to 20 ° C., followed by stirring for 3 hours. After cooling to an internal temperature of 4 ° C., 826 mL of acetic acid was gradually added to keep the internal temperature at 12 ° C. To this solution, 65 mL of nitrosylsulfuric acid (Aldrich product) was added dropwise. After stirring for 3 hours, 21.3 g of urea was added. After stirring for 2 hours, the mixture was added dropwise to 1300 mL (internal temperature: 4 ° C.) of 52.4 g of a separately prepared compound 1 in 52.4 g. After stirring at an internal temperature of 4 ° C. for 15 minutes, the temperature was raised to room temperature. The precipitated crystals were separated by filtration, dispersed in 1000 mL of ion-exchanged water, and stirred with heating at an internal temperature of 85 ° C. for 1 hour. After cooling to room temperature, the crystals separated by filtration were washed with 1000 mL of ion-exchanged water and then with 500 mL of methanol. After drying at 75 ° C., 137.8 g (yield 81.6%) of a yellow powder was obtained.

Subsequently, 43.5 g of this yellow powder was dispersed in 87 mL of methanol, 87 mL of isopropanol, and 44 mL of ion-exchanged water, and 44 mL of 2 mol / L potassium hydroxide aqueous solution and 20 mL of ion-exchanged water were added at room temperature. Then, 40 mL of 2 mol / L potassium hydroxide aqueous solution was dripped, maintaining the reaction liquid at pH 13.6 or less. Methanol (448 mL) was added dropwise to the reaction solution, and the precipitated crystals were collected by filtration and washed with 200 mL of methanol. Crystals dried at 75 ° C. were dissolved in 505 mL of ion-exchanged water, and the solution was adjusted to pH 8.5 with 40 mL of 1 mol / L hydrochloric acid aqueous solution. Subsequently, 1089 mL of methanol was added dropwise, followed by 817 mL of isopropanol, and the precipitated crystals were separated by filtration and washed with 300 mL of isopropanol. After drying at 75 ° C., 40.0 g (yield 79.3%) of azo compound 20 was obtained. λmax: 456.7 nm (H ₂ O), ε: 59900
[Example 4]

Azo compound 1 was produced by the same production method as in Synthesis 3 except that the amount of 95% sulfuric acid used in Synthesis 3 was changed to 16.9 g.
[Examples 5 to 25]

  Compound 3 (amino compound) used in Synthesis 3 and its use amount and Compound 1 (Compound represented by the general formula (1)) and its use amount were changed to those described in Tables 1 to 4 except that they were changed to the contents shown in Tables 1 to 4 Various azo compounds were produced by the same production method.

<Synthesis of Azo Compound by Step (a), Step (b), Step (c)>
[Example 26]

(Synthesis of azo compound 1 including step (c))
Scheme 4

(Synthesis of Azo Compound 1) After stirring 9.2 g of 95% sulfuric acid at an internal temperature of 10 ° C., 23.6 g of acetic acid was added to keep the internal temperature at 10 ° C. or lower. 4.9 mL of 40 mass% nitrosyl sulfuric acid (made by Aldrich) was dripped there. Further, 7.3 g of Compound A-1: was added in portions and stirred at an internal temperature of 0-5 ° C. for 1.5 hours. To this reaction solution, 0.6 g of urea was added, and stirring was further continued for 0.5 hours (diazonium compound preparation solution). A diazonium compound preparation solution was added dropwise at an internal temperature of 20 ° C. or lower to a compound prepared by adding 5.7 ml of a methanol solution of 1.6 g of potassium hydroxide (internal temperature of 20 ° C.) to 68 ml of a methanol solution of 5.4 g of separately prepared compound 1. . After dropping, the temperature was raised to 20 ° C., stirred for 1 hour, cooled to 10 ° C., and 26.3 ml of a separately prepared methanol solution of 7.4 g of potassium hydroxide was added at 20 ° C. or less. The temperature was raised to 50 ° C. and stirred for 1 hour while maintaining the temperature. The pH at this time was 0.6. Thereafter, the mixture was cooled to 30 ° C. or less over 1 hour, and the precipitated yellow crystals (azo compound 0) were subjected to suction filtration using ADVANTEC filter paper 70 mm (type 2). Filtration time is 30 seconds. The production rate of azo compound 0 is 93.2% (HPLC area%).
The obtained crystals were suspended in 130 ml of ion-exchanged water, heated to 70 ° C., stirred for 1 hour, and suction filtered to obtain 10.8 g (yield 94.0%). Thereafter, azo compound 1 could be obtained by the same method as in Synthesis 3. In addition, the filterability when not performing (c) process required time of 431 second. From this result, the effect of the step (c) became clear.
[Example 27]

(Synthesis of azo compound 1 when the salt state of the raw material is different)
Scheme 4

(Synthesis of Compound 1-1)
500 mL of water was added to 20.0 g of intermediate 1 synthesized according to the method described in JP-A-2006-57076 and 34.9 g of pivaloyl acetonitrile, and the mixture was stirred at room temperature (internal temperature 24 ° C., pH 5.08). 56 mL of 1M aqueous hydrochloric acid was added to the reaction mixture (internal temperature 25 ° C., pH 2.81 at the time of preparation). After stirring with heating at an internal temperature of 50 ° C. for 8 hours (internal temperature 50 ° C., pH 1.20), 27-28 mL of an 8M aqueous potassium hydroxide solution was slowly added dropwise, and the reaction solution became homogeneous (internal temperature 50 ° C., pH 8 .7-8.9). Further, after stirring for 30 minutes at an internal temperature of 50 ° C., 13.5 mL of a 12M hydrochloric acid aqueous solution was slowly added dropwise to precipitate crystals (internal temperature of 50 ° C., pH 6.5 to 6.7). The crystals were collected by filtration, washed with 400 mL of water, and dried to obtain 40.2 g of compound 1-1 (isolated yield 85.1%, HPLC purity 97.1%).
Scheme 5

(Synthesis of Azo Compound 1) Synthesis of azo compound 1 using compound A-1 instead of compound A and compound 1-1 instead of compound 1 is shown below.
After stirring 9.2 g of 95% sulfuric acid at an internal temperature of 10 ° C., 23.6 g of acetic acid was added to keep the internal temperature at 10 ° C. or lower. 4.9 mL of 40 mass% nitrosyl sulfuric acid (made by Aldrich) was dripped there. Further, 7.3 g of Compound A-1: was added in portions and stirred at an internal temperature of 0-5 ° C. for 1.5 hours. To this reaction solution, 0.6 g of urea was added, and stirring was further continued for 0.5 hours (diazonium compound preparation solution). To the separately prepared compound 1-1: 4.52 g of methanol solution 73.5 ml, the diazonium compound preparation solution was dropped at an internal temperature of 20 ° C. or less. After dropping, the temperature was raised to an internal temperature of 20 ° C. and stirred for 1 hour. After cooling to 10 ° C., 26.3 ml of a methanol solution of 7.4 g of potassium hydroxide prepared separately was added at 20 ° C. or lower, and the temperature was raised to an internal temperature of 55-60 ° C. and stirred for 1 hour. Thereafter, the mixture was cooled to 30 ° C. or less over 1 hour, and the precipitated yellow crystals (azo compound 0) were subjected to suction filtration using ADVANTEC filter paper 70 mm (type 2). Filtration time is 30 seconds. The obtained crystals were suspended in 130 ml of ion-exchanged water, heated to 70 ° C., stirred for 1 hour, and suction filtered to obtain 11.3 g (yield 92%). Thereafter, the azo compound 1 was obtained in the same manner as in Example 3.
[Examples 28 and 29]

  The compound A-1 used in Example 26 and its use amount, and the compound 1 and its use amount were changed to the raw material corresponding to the azo compounds 20 and 21 and the use ratio amounts described in Example 3 and Table 3. Was synthesized in the same manner as in Example 26.

(Comparative Example 1)
The reaction was carried out in the same manner as in Example except that the acid used in Example 3 was changed to 95% sulfuric acid / acetic acid to dilute hydrochloric acid and nitrosylsulfuric acid to sodium nitrite aqueous solution. After coupling, azo compound 1 was not produced.

  From the table, it can be seen that the yield is high in the examples of the present invention. Further, when the step (C) is included, the reduction of the filtration time is remarkable.

Claims (13)

(A) a step of mixing an acid or mixed acid and an amino compound having an acidity function H ₀ of the diazotizing agent and Hammett of −1.00 or less; a diazonium compound adjusting liquid obtained in the step (a); And (b) a step of mixing the compound represented by (1).

In the above general formula (1):
Each X independently represents a hydrogen atom or a substituent, and this substituent may further have a substituent.
Y represents —OR ¹ , —NR ² R ³ , or —SR ⁴ , and R ¹ represents a hydrogen atom, an alkali metal ion, an organic cation, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic ring. R ^{2 to} R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. These groups may further have a substituent.
Z represents —OM or —NR ⁵ R ⁶ . Where M represents a hydrogen atom or a metal ion, and R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group, an alkyl or arylcarbonyl group, Or an alkyl or arylsulfonyl group; These groups may further have a substituent.
G represents a hydrogen atom or a halogen atom.
Q represents an atomic group constituting a nitrogen-containing heterocyclic ring together with a carbon atom directly connected to pyrazole.
n, s, and t represent integers satisfying the relationships of 1 ≦ n ≦ 3, 0 ≦ s ≦ 2, 0 ≦ t ≦ 1, and n + s + t = 3.   2. The method for producing an azo compound according to claim 1, wherein in formula (1) in claim 1, the nitrogen-containing heterocyclic ring that Q constitutes is a 5- or 6-membered aromatic nitrogen-containing heterocyclic ring. The method for producing an azo compound according to claim 1, wherein the general formula (1) is the following general formula (2).

In the general formula (2):
Each X independently represents a hydrogen atom or a substituent, and this substituent may further have a substituent.
Y represents —OR ¹ , —NR ² R ³ , or —SR ⁴ , and R ¹ represents a hydrogen atom, an alkali metal ion, an organic cation, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic ring. R ^{2 to} R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. These groups may further have a substituent.
Z represents —OM or —NR ⁵ R ⁶ . M represents a hydrogen atom or a metal ion, and R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkyl or arylcarbonyl group, or Represents an alkyl or arylsulfonyl group; These groups may further have a substituent.
G represents a hydrogen atom or a halogen atom.
n, s, and t represent integers satisfying the relationships of 1 ≦ n ≦ 3, 0 ≦ s ≦ 2, 0 ≦ t ≦ 1, and n + s + t = 3.   In the said General formula (1) or General formula (2), n is 2 or 3, The manufacturing method of the azo compound as described in any one of Claims 1-3 characterized by the above-mentioned. The said general formula (2) is the following general formula (3), The manufacturing method of the azo compound as described in any one of Claims 1-4 characterized by the above-mentioned.

In the general formula (3):
X ¹ and X ² each independently represent a hydrogen atom or a substituent, and this substituent may further have a substituent.
Y represents —OR ¹ , —NR ² R ³ , or —SR ⁴ , and R ¹ represents a hydrogen atom, an alkali metal ion, an organic cation, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic ring. R ^{2 to} R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group. These groups may further have a substituent.
Z ¹ and Z ² each independently represent —OM or —NR ⁵ R ⁶ . M represents a hydrogen atom or a metal ion, and R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkyl or arylcarbonyl group, or Represents an alkyl or arylsulfonyl group; These groups may further have a substituent.   The said amino compound is an amino pyrazole derivative and its salt, The manufacturing method of the azo compound as described in any one of Claims 1-5 characterized by the above-mentioned. The said amino compound is General formula (4), The manufacturing method of the azo compound as described in any one of Claims 1-6 characterized by the above-mentioned.

In the general formula (4), R ¹¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group or a heterocyclic group, and R ¹² represents a hydrogen atom or a Hammett substituent constant. σp value represents a substituent having a value of 0.20 or more, and R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a substituent. Two or more of R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ represent an ionic hydrophilic group or a monovalent group having an ionic hydrophilic group as a substituent. However, the case where R ¹³ and R ¹⁶ are simultaneously a sulfo group is excluded. In the general formula (4), R ¹² is a cyano group, —SO ₂ CH ₃ or —SO ₂ Ph, The method for producing an azo compound according to claim 7. The method for producing an azo compound according to claim 7 or 8, wherein in the general formula (4), R ¹² is a cyano group.   The method for producing an azo compound according to any one of claims 1 to 9, wherein in the step (a), the diazotizing agent is nitrosylsulfuric acid.   The said (a) process WHEREIN: An acid is a sulfuric acid, phosphoric acid, or methanesulfonic acid, and a mixed acid is a mixed acid of these acids and an acetic acid, It is any one of Claims 1-10 characterized by the above-mentioned. A method for producing an azo compound.   The method for producing an azo compound according to any one of claims 1 to 11, further comprising a step (c) of stirring the mixed liquid obtained in the step (b) while heating. The azo compound according to the following general formula (5) obtained by the production method according to any one of claims 1 to 12.

In the general formula (5):
Q ¹ and Q ² each independently represents an aromatic hydrocarbon ring group, a non-aromatic hydrocarbon ring group, an aromatic heterocyclic group or a non-aromatic heterocyclic group, which may have a substituent, and X ¹ and X ² each independently represents a hydrogen atom or a substituent, and this substituent may further have a substituent.
Y represents —OR ¹ , and R ¹ represents a hydrogen atom or a metal ion. Z ¹ and Z ² each independently represent —OM or —NR ⁵ R ⁶ . M represents a hydrogen atom or a metal ion, and R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkyl or arylcarbonyl group, or Represents an alkyl or arylsulfonyl group; These groups may further have a substituent.